EP2597139A1 - Biodiesel stabilisé contre l'oxydation - Google Patents

Biodiesel stabilisé contre l'oxydation Download PDF

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Publication number
EP2597139A1
EP2597139A1 EP11190450.4A EP11190450A EP2597139A1 EP 2597139 A1 EP2597139 A1 EP 2597139A1 EP 11190450 A EP11190450 A EP 11190450A EP 2597139 A1 EP2597139 A1 EP 2597139A1
Authority
EP
European Patent Office
Prior art keywords
biodiesel
baynox
oil
ppm
natural oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11190450.4A
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German (de)
English (en)
Inventor
Axel Dr. Ingendoh
Uwe Dr. Böger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Priority to EP11190450.4A priority Critical patent/EP2597139A1/fr
Priority to PCT/EP2012/073509 priority patent/WO2013076266A1/fr
Publication of EP2597139A1 publication Critical patent/EP2597139A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/62—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to oxidation-stabilized biodiesel, a process for the production thereof and its use.
  • Biodiesel or fatty acid alkyl ester is increasingly being used as an alternative to conventional diesel fuel. It has established itself as a regenerative and CO 2 neutral fuel of the first generation.
  • the preparation is almost exclusively by transesterification of vegetable oils (fatty acid glycerides), such as palm oils, rapeseed oil, soybean oil or sunflower oil, with methanol or ethanol to fatty acid methyl or ethyl esters by catalysis of bases, such as NaOH, KOH, sodium or potassium.
  • vegetable oils fatty acid glycerides
  • palm oils such as palm oils, rapeseed oil, soybean oil or sunflower oil
  • bases such as NaOH, KOH, sodium or potassium.
  • Vegetable oils in contrast to mineral oils, are inferior to stronger aging processes. The increased oxidation and the formation of free fatty acids are essentially responsible for this aging. Therefore, the use of antioxidants has become more and more established. For example, this is off EP-A 1736528 the use of substituted alkylphenols known. These are added in concentrations of 0.005 to 2.0 wt.% To the biodiesel.
  • BHT butylated hydroxytoluene
  • the object of the present invention was therefore to provide an improved oxidation-stable biodiesel, which allows manufacturers a wider time window during processing and storage.
  • butylhydroxtoluene (BHT) prefers.
  • the compounds of formula (I) are commercial compounds, e.g. available from Lanxess GmbH under the trade name Baynox® (Vulkanox® BHT) or Baynox® plus (Vulkanox® BKF).
  • vegetable oils such as preferably rapeseed oil, soybean oil, palm oils or other vegetable oils, but also used cooking oils, eg. B. from food production, and algae oil and animal fats understood. Chemically, these natural oils are fatty acid glycerides. Vegetable oil is preferably used. Particularly preferred are vegetable oils, such as rapeseed oil or soybean oil.
  • doping is preferably understood to mean the introduction of at least one compound of the formula (I) in a natural oil.
  • the introduction is preferably carried out by mixing until dissolution of the compound of formula (I).
  • the doping of the natural oil with at least one compound of formula (I) is preferably carried out by mixing, preferably stirring at least one compound of formula (I) in crystalline form and / or by stirring a concentrated solution of 10 to 20 wt% of Compound of formula (I) in natural oil and / or a concentrated solution of 20 to 50% by weight of the compound of formula (I) dissolved in biodiesel in the natural oil at a temperature of preferably 40 to 50 ° C.
  • mixing units are in principle all known stirrers, preferably axial, radial or tangential stirrers, as described in Wilke et al., Mixing Technology Principles of process engineering and apparatus. Dr. Alfred Wilsonhig Verlag Heidelberg, 2nd edition, 1991, pages 92 to 97 , suitable..
  • the amounts of the compound of the formula (I) are preferably 0.005 to 2.0% by weight.
  • biodiesel is fatty acid methyl ester (FAME) and / or a fatty acid ethyl ester (FAEE), ie, the alkanol used in the transesterification either Methanol or ethanol. It is also possible to use mixtures of FAME or FAEE, ie in this case an alkanol mixture of methanol and ethanol is used.
  • FAME fatty acid methyl ester
  • FAEE fatty acid ethyl ester
  • the transesterification is preferably carried out alkaline.
  • the natural oil preferably rapeseed oil or soybean oil
  • the alkanol preferably methanol or ethanol
  • the catalyst preferably NaOH, KOH, sodium methoxide NaOCH 3 or other methanolates dissolved in methanol, presented, and to temperatures in the range heated by preferably 50 to 80 degrees Celsius.
  • the ratio of natural oil to alkanol is preferably 1200g to 260g.
  • the reaction solution is then stirred preferably at temperatures of 50 to 80 ° C for a period of about 80 to 180 minutes. As mixing units are all known stirrers suitable. Subsequently, the phases of the reaction solution are separated and the biodiesel phase washed with water. From the Biodieselphase then the residual water, z. B. by distillation (painting) removed. Usually obtained with the process according to the invention biodiesel with a yield of about 90%.
  • the catalyst preferably NaOH, KOH, sodium methoxide NaOCH 3 or other methanolates dissolved in methanol, is added to the methanol and dissolved.
  • the amount of catalyst is preferably 0.5-1.5 wt%.
  • the methanol is added beyond the stoichiometric ratio of oil (glycerol ester) to alcohol to shift the reaction to the side of the methyl ester.
  • the lighter phase contains biodiesel with admixtures of methanol, the lower phase mainly glycerol and by-products.
  • the lower phase of the biodiesel is washed twice with 10 to 30 wt.% Water to remove traces of alkali and the methanol and either distilled or otherwise dried.
  • the glycerol phase contains excess methanol as well as most by-products of the process.
  • the present invention also relates to the use of the inventively stabilized biodiesel as a fuel.
  • the end of aging or oxidative stability was indicated by a steep increase in the conductivity.
  • the time to reach the break point is referred to as the induction period and serves as a measure of the aging stability.
  • Example 1 Storage stability of rapeseed oil / soybean oil after treatment with Baynox® for comparison
  • Rapeseed oil or soybean oil was used in which no, or 500 ppm or 1000 ppm Baynox® at 40 ° C was stirred.
  • Rapeseed oil without antioxidant (V1) has the lowest oxidation stability after 28 days storage at 40 ° C. Rapeseed oil without antioxidant aged significantly faster. By adding 500 ppm of Baynox® to the rapeseed oil alone, the oxidation stability is twice as high after 28 days. The aging process is significantly reduced.
  • soybean oil without antioxidant V4
  • the direct addition of Baynox® to soybean oil has also weakened the aging process of soybean oil.
  • Soybean oil with an initial dosage of 500 ppm Baynox® as an antioxidant has a storage time of 28 days, a 65% higher oxidation stability than soybean oil without antioxidant.
  • An initial doping of 1000 ppm with Baynox® increases the oxidation stability by 125%.
  • Example 2 Oxidation stability of rapeseed oil / sajo oil after transesterification and treatment with Baynox®
  • the samples V1 to V6 are transesterified with 146.8 g of methanol at 65 ° C in the presence of 4.09 g of sodium hydroxide.
  • biodiesel from natural oils to which Baynox® is added directly before the transesterification into the vegetable oil, has a significantly better quality (cf. Figur1 ) as biodiesel to which the antioxidant was added only after the transesterification.
  • V7 and V8 showed the oxidation stability of biodiesel made from undoped rapeseed oil. This had an initial oxidation stability of 5.7 hours. After adding 500 ppm of Baynox®, the oxidation stability increased to 8.2 hours. V9 and V10 showed the oxidation stabilities of the biodiesel, which from those with initially 500 ppm or 1000 ppm of doped rapeseed oil was produced. With a residual content of 341 ppm Baynox® V9 showed a higher oxidation stability than V8 with 500 ppm Baynox®. This effect can be seen even more clearly in V10, which was produced from rapeseed oil doped with 1000 ppm Baynox®.
  • V11 demonstrated the oxidation stability of the biodiesel made from the undoped soybean oil and had an initial oxidation stability of 0.8 hours. After addition of 500 ppm Baynox®, the oxidation stability increased to 2.4 hours. Even with 1000 ppm Baynox® V11 did not reach the European biodiesel standard of 6 hours oxidation stability.
  • V13 and V14 the oxidation stabilities of the biodiesel prepared from the soybean oil initially doped with 500 ppm and 1000 ppm, respectively, were measured.
  • Example 3 (comparison) Storage stability of rapeseed oil without Baynox®
  • Rapeseed oil was stored open at room temperature for 33 weeks.
  • Example 4 (comparison) Storage stability of rapeseed oil with Baynox®
  • Rapeseed oil was mixed with 1000 ppm Baynox® and stored open at room temperature for 33 weeks.
  • Rapeseed oil with an initial content of 1000 ppm Baynox® still has an oxidation stability of 4.4 hours after a storage time of 33 weeks.
  • Example 5 (Comparison) Production of biodiesel from aged rapeseed oil without Baynox®
  • Rapeseed oil was stored open at room temperature for 33 weeks (analogous to Example 3). Biodiesel produced therefrom by alkaline transesterification only achieved an oxidation stability of 0.6 hours. Even with the addition of large amounts of antioxidant (up to 2500 ppm Baynox®), it is no longer possible to produce a biodiesel that meets the specifications of this rapeseed oil.
  • Example 6 (Inventive) Production of biodiesel from aged Baynox®-containing rapeseed oil

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Fats And Perfumes (AREA)
EP11190450.4A 2011-11-24 2011-11-24 Biodiesel stabilisé contre l'oxydation Withdrawn EP2597139A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP11190450.4A EP2597139A1 (fr) 2011-11-24 2011-11-24 Biodiesel stabilisé contre l'oxydation
PCT/EP2012/073509 WO2013076266A1 (fr) 2011-11-24 2012-11-23 Procédé de fabrication d'un biodiesel stabilisé à l'oxydation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP11190450.4A EP2597139A1 (fr) 2011-11-24 2011-11-24 Biodiesel stabilisé contre l'oxydation

Publications (1)

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EP2597139A1 true EP2597139A1 (fr) 2013-05-29

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006043281A1 (fr) * 2004-10-20 2006-04-27 Council Of Scientific And Industrial Research Procédé amélioré pour la préparation d'ester méthylique d'acide gras (biodiesel) à partir de triglycéride d'huile via une transestérification
EP1736528A2 (fr) 2005-04-04 2006-12-27 Degussa GmbH Procédé d'augmentation de la stabilité à l'oxydation d'un biodiesel.
EP2311929A1 (fr) * 2009-10-19 2011-04-20 Lurgi GmbH Procédé de préparation d'huile brute légèrement saponifiable d'origine végétale ou animale pour le recyclage en biodiesel

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006043281A1 (fr) * 2004-10-20 2006-04-27 Council Of Scientific And Industrial Research Procédé amélioré pour la préparation d'ester méthylique d'acide gras (biodiesel) à partir de triglycéride d'huile via une transestérification
EP1736528A2 (fr) 2005-04-04 2006-12-27 Degussa GmbH Procédé d'augmentation de la stabilité à l'oxydation d'un biodiesel.
EP2311929A1 (fr) * 2009-10-19 2011-04-20 Lurgi GmbH Procédé de préparation d'huile brute légèrement saponifiable d'origine végétale ou animale pour le recyclage en biodiesel

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE CAPLUS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 1 January 2010 (2010-01-01), INGENDOH, AXEL: "Protection of biodiesel against oxidation", XP002674714, Database accession no. 2010:758654 *
INGENDOH, AXEL: "Protection of biodiesel against oxidation", LIPID TECHNOLOGY, vol. 22, no. 4, 1 January 2010 (2010-01-01), pages 83 - 86 *
WILKE ET AL.: "Rührtechnik Verfahrenstechnische und apparative Grundlagen", 1991, DR. ALFRED HÜTHIG VERLAG, pages: 92 - 97

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